SW-846 Update V FOUR - i Revision 5 

October 2012 

CHAPTER FOUR 

TABLE OF CONTENTS 

Section Page 

 

4.1 SAMPLING CONSIDERATIONS 1 

4.2 SAMPLE PREPARATION METHODS 13 

4.3 DETERMINATION OF ORGANIC ANALYTES 14 

4.4 IMMUNOASSAY METHODS 17 

4.5 MISCELLANEOUS SCREENING METHODS 18 

4.6 REFERENCES 19 

Table 

4-1 RECOMMENDED SAMPLE CONTAINERS, PRESERVATION 

TECHNIQUES, AND HOLDING TIMES 

9 

Appendix A SUMMARY OF UPDATES/CHANGES IN CHAPTER 4 21 
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October 2012 

CHAPTER FOUR 

 ORGANIC ANALYTES

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for guidance 

on the allowed flexibility in the choice of apparatus, reagents, and supplies. In addition, unless 

specified in a regulation, the use of SW-846 methods is not mandatory in response to Federal 

testing requirements. The information contained in this chapter is provided by EPA as guidance 

to be used by the analyst and the regulated community in making judgments necessary to meet 

the data quality objectives or needs for the intended use of the data. 

4.1 SAMPLING CONSIDERATIONS 

4.1.1 Introduction 

 Following the initial and critical step of designing a sampling plan (Chapter Nine) is 

the implementation of that plan such that a representative sample of the solid waste (or 

material) is collected. Once the sample has been collected it must be stored and preserved 

to maintain the chemical and physical properties that it possessed at the time of collection. 

The sample matrix, type of containers and their preparation, analytes of interest, 

preservation techniques, and sample holding time must be thoroughly examined in order to 

maintain the integrity of the samples. This section highlights practices relevant to 

maintaining sample integrity and representativeness from the time of sampling until 

analysis is complete. This section is, however, applicable primarily to trace analyses. Some 

of these considerations may be less relevant for source level samples. 

4.1.2 Sample Handling and Preservation: General Considerations 

This following sections deal separately with volatile organic chemicals (VOCs) and 

semivolatile organic chemicals (SVOCs). Refer to Chapter Two and Table 4-1 of this 

section for recommended sample containers, sample preservation, and holding time 

information. The guidelines in Table 4-1 are intended to improve chemical stability in the 

sample matrix between the time of sample collection and laboratory preparation / analysis 

by minimizing loss of the analytes of interest from the sample container and limiting 

biological and/or chemical degradation (e.g., hydrolysis) (Sec. 4.6 Refs 1, 3-6). Sample 

preservation recommendations for analysis of organic chemicals almost always include 

refrigeration or freezing and may also include chemical preservation (e.g., addition of pH 

modifier). Improper handling, preservation, and storage of samples can negatively impact 

the representativeness of the field sample data. 
SW-846 Update V FOUR - 2 Revision 5 

October 2012 

The preservation and holding time information presented in Table 4-1 does not 

represent EPA requirements, but rather is intended solely as guidance. Selection of 

preservation techniques and applicable holding times should be based on all available 

information, including the properties of the analytes of interest for the project, their 

anticipated concentration levels, the composition of the sample matrix itself, and the stated 

project-specific data quality objectives. A shorter holding time may be appropriate if the 

analytes of interest are reactive (e.g., 2-chloroethyl vinyl ether, acrylamide) or the sample 

matrix is complex (e.g., wastewater). Conversely, a longer holding time may be appropriate 

if it can be demonstrated that the analytes of interest are not adversely affected from 

preservation, storage and analyses performed outside the recommended holding times. 

Prior to collecting samples for analysis, the project team may consider existing information 

and data regarding analyte stability or conduct field screening for the samples to be 

collected in order to determine how best to preserve sample integrity for the analytes of 

interest. The use of site-specific performance evaluation material is a high confidence 

mechanism to ensure reliability of project data. The references in Sec. 4.6 provide 

examples of study designs that may be useful for this purpose. 

4.1.3 Sample Handling and Preservation for Volatile Organics 

 4.1.3.1 VOC Sample Containers 

 The containers used for collecting VOC samples are frequently volatile 

organics analysis (VOA) vials that are directly compatible with the equipment used 

for sample preparation and analysis in the laboratory. Use of these containers for 

sampling helps minimize loss of VOCs resulting from opening sample containers 

and/or transferring materials from one container to another. Certified pre-cleaned 

VOA vials are commonly used as sample containers for VOCs and are 

commercially available from a number of vendors. The vials should be absent of 

burrs around the caps that might prevent the vial from sealing, and septa should be 

lined with a PTFE layer of sufficient thickness to limit diffusion of VOCs out of the 

vials during storage. PTFE thicknesses of 0.13 to 0.25 mm have been shown to be 

effective. See reference # 18 in Sec. 4.6 below and Sec. A.8 in Method 5035A for 

more detail. If they are suspected of being a source of interferences, VOA vials 

and unpunctured septa should be washed with soap and water and rinsed with 

distilled de-ionized water. After thoroughly cleaning the vials and septa, they should 

be placed in an oven and dried at 100 °C for approximately one hour. 

 NOTE: Heating the septa for extended periods of time (i.e., more than one hour) 

 or at higher temperatures should be avoided, because the silicone begins to slowly 

 degrade at 105 °C). Also, punctured silicone backed PTFE lined septa should 

 generally not be reused, because some VOCs have high affinity for the 

 silicone material, and puncturing the PTFE septum face exposes the gas phase vial 

 contents to the silicone backing material, causing loss of certain VOCs depending 

 on length of exposure time and vial temperature. 

Air-tight, sealable coring devices (e.g., En CoreTM, Core N’ OneTM or 

equivalent) may also be useful for collection and storage of cohesive soil samples 

for VOC analysis. These devices are designed to limit loss of VOCs from samples 

during cold storage and shipping over a limited time frame and for quantitative 

transfer of solids and associated VOCs into VOA vials for immediate analysis or 

further preservation. Their use during field sampling of solids helps reduce or 

eliminate the need to handle solvents or chemical preservatives in the field and 

eliminates some shipping restrictions on field samples that may otherwise contain 
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October 2012 

flammable solvents (e.g., methanol). Additional information regarding stability 

studies of VOCs in solid materials stored in sealable coring devices is contained in 

the Sec. A.7 of the appendix of Method 5035A and is described in more detail in the 

sources referenced therein. An ASTM standard practice for use of the En CoreTM

type samplers is also included in the references in Sec. 4.6 below. 

4.1.3.2 VOC Sample Collection: 

When transferring samples into vials, liquids and solids should be 

introduced gently to minimize agitation which might drive off volatile compounds. At 

least two replicate VOA vials should be taken and labeled immediately for each 

collected field sample. They should not be filled near a running motor or any type of 

exhaust system because discharged fumes and vapors may contaminate the 

samples. Replicate vials from a single sampling point may be sealed together in a 

single plastic bag, but different samples should be segregated into separate plastic 

bags to prevent contamination of samples with little to no VOCs from those with 

high concentrations. Sample containers may also become contaminated by 

diffusion of VOCs into the vials through the septa from the surrounding environment 

during shipment and storage. To monitor for this potential source of contamination, 

a trip blank prepared from organic-free reagent water (as defined in Chapter One) 

should be maintained with the samples throughout sampling, shipping, and storage. 

Including activated carbon in the bags containing the sample vials may help reduce 

concerns related to these potential sources of sample contamination. 

Improper vial sealing (e.g., due to solids retained on the vial threads) and 

improper tightening of caps or closing of sealable coring devices are primary factors 

in the loss of volatiles due to sample collection activities. Sealing surfaces and any 

closure threads should be inspected to ensure they are free of debris prior to 

container closure. 

Procedures should also be established for selection and appropriate use 

of sample collection devices (i.e., bailer, coring tool, etc.) including appropriate 

decontamination measures. If the sample comes in contact with the sampling 

device, organic free reagent water may be run through the device and tested as a 

field blank. 

 In general, liquid samples should be poured into vials without introducing 

any air bubbles into the samples as vials are filled. Should bubbling occur as a 

result of violent pouring, the sample should be poured out and the vial refilled. The 

vials should be completely filled at the time of sampling, so that when the septum 

cap is fitted and sealed and the vial is inverted, no headspace is visible. The sample 

should be hermetically sealed in the vial at the time of sampling, and not opened 

prior to analysis to preserve its integrity. 

4.1.3.3 VOC Sample Preservation and Holding Times: 

Samples containing analytes that can be subject to biological degradation 

need to be preserved as soon as possible (preferably in the field) to avoid the loss 

of target analytes. Refrigeration or freezing is a primary means of sample 

preservation, because rates of biotic and abiotic degradation decrease with 

decreasing temperature, and VOCs are also less volatile at lower temperature. 

Samples containing analytes that are most subject to biological degradation (e.g., 

aromatic hydrocarbons) also should be chemically preserved (e.g., by addition of 
SW-846 Update V FOUR - 4 Revision 5 

October 2012 

acid), unless they are analyzed immediately. Chemical preservation may be 

inappropriate for highly reactive compounds, e.g., 2-chloroethyl vinyl ether, 

acrylamide, etc., since it may accelerate loss by rapid chemical reaction. Aqueous 

samples containing free chlorine should also be preserved with a dechlorinating 

agent in order to minimize formation of trihalomethanes and other possible 

chemical reactions. 

Although VOA samples may be held for up to 7 days unpreserved or 14 

days or longer preserved, it is generally not recommended as good laboratory 

practice to hold them that long. VOA samples should be run as soon as possible 

after receipt by the laboratory. Samples in which highly reactive compounds (e.g., 

2-chloroethyl vinyl ether, acrylamide, etc.) are analytes of interest should be 

analyzed as soon as they are received in the laboratory. 

4.1.4 Sample Handling and Preservation for Semivolatile Organics, Including 

Pesticides, PCBs and Herbicides 

 4.1.4.1 Sample Containers for Analysis of Semivolatile Organics 

The containers specified for samples intended for analysis of semivolatile 

organic chemicals (SVOCs) are typically constructed of glass with PTFE lined 

threaded caps. In situations where PTFE liners are not available, solvent-rinsed 

aluminum foil may be used as a liner. However, acidic or basic samples may react 

with the aluminum foil, causing eventual contamination of the sample. Use of new, 

disposable pre-cleaned and certified containers reduces concerns about 

contamination from reusing sample containers. Plastic containers or plastic lids 

without PTFE liners should not be used for storage of samples due to potential 

contamination by phthalate esters and other hydrocarbons within the plastic or 

absorption of any chemicals of concern in the native sample into the container 

material. If sample containers are suspected of being a source of interferences 

particularly for low level analysis, they should be soap and water washed followed 

by rinsing with solvent(s) appropriate for the analytes of interest. See Sec. 4.1.6 for 

specific instructions on glassware cleaning). Caps may be cleaned by solvent 

rinsing or replaced with new ones. Monitoring for contamination introduced from 

sample containers should be accomplished through preparation and analysis of a 

method blank. 

 4.1.4.2 Sample Collection for SVOCs 

 Sample containers should be filled with care so as to prevent any portion of 

the collected samples from coming in contact with the sampler's gloves, potentially 

leading to sample contamination. Samples should not be collected or stored in the 

presence of exhaust fumes. If the sample comes in contact with the sampling 

device, run organic free reagent water through it and test this water as a field blank. 

4.1.4.3 Sample Preservation and Holding Times for SVOCs 

Field samples to be analyzed for SVOCs are typically preserved by 

refrigeration or freezing. In order to minimize opportunities for the most labile 

SVOCs to degrade, these samples are typically recommended to be solvent 

extracted shortly after being taken, within 7-14 days for many classes of chemicals. 

However, some classes of SVOCs, like poly-chlorinated biphenyls and 

polychlorinated dibenzodioxins and dibenzofurans are very recalcitrant and do not 
SW-846 Update V FOUR - 5 Revision 5 

October 2012 

readily degrade during refrigerated storage. Sample matrices to be analyzed for 

these SVOCs have no maximum recommended holding time. Depending on the 

composition of the sample matrix and the levels of concern for the target analytes, 

other classes of SVOCs (e.g., polycyclic aromatic hydrocarbons) may also be 

stable in refrigerated or frozen storage for longer than the maximum holding time 

recommended in Table 4-1 (see Reference #12 in Sec. 4.6 below). However, the 

composition of the sample matrix can be an important determinant of chemical 

stability, and minimizing the holding time between sampling and solvent extraction 

is generally a good practice to obtain representative data. 

Solvent extracts of samples should be carefully maintained. Solvent 

extraction generally stabilizes SVOCs, because the chemicals are typically 

physically removed from the sample matrix, and some loss mechanisms are 

eliminated (i.e., biological degradation). Holding times of 40 days are recommended 

for solvent extracts for most classes of SVOCs. Many analytes of interest may be 

stable in solvent for a longer time period even in extracts of complex matrices, but 

problems maintaining small volumes of very volatile solvent extracts preclude 

storage of extracts indefinitely, and some SVOCs may still chemically degrade or 

may be slightly volatile in certain solvents. 

Freezing solvent extracts particularly of complex sample matrices may 

cause precipitation of solids resulting from interaction of some co-extracted sample 

matrix components. Storing extracts at 0 to 6 oC may limit problems resulting from 

analyzing extracts containing precipitated solids, like contaminating or clogging the 

injector syringe or introducing insoluble components into the flow pathway of the 

mobile phase. One way to remove precipitated solids from a solvent extract is by 

filtration with a sub-micron particle size filter made of inert material (e.g., PTFE). As 

with other preparation steps, batch QC samples should be subjected to the same 

filtration procedure as the field samples in order to assess the cumulative impact of 

all sample preparation steps on analyte recovery and evaluate the potential for 

contamination resulting from all reagents, and other materials that come into 

contact with the samples. 

4.1.5 Safety 

The methods listed in this chapter do not address all safety issues associated with 

their use. The laboratory is responsible for maintaining a safe work environment and a 

current awareness file of OSHA regulations regarding the safe handling of the chemicals 

used in these methods. A reference file of material safety data sheets (MSDSs) should be 

available to all personnel involved in these analyses. 

Safety should always be the primary consideration in the collection and analysis of 

samples. A thorough understanding of the waste production process, as well as all of the 

potential hazards of the waste itself, should be investigated whenever possible. The site 

should be evaluated just prior to sampling to determine whether any additional safety 

measures are necessary. Minimum protection of gloves and safety glasses should be worn 

to prevent sample contact with the skin and eyes. A respirator should be worn even when 

working outdoors if organic vapors are present. More hazardous sampling missions may 

require the use of supplied air and special clothing. 
SW-846 Update V FOUR - 6 Revision 5 

October 2012 

4.1.6 Cleaning of Reusable Glassware 

In order to successfully analyze samples containing components in the parts per 

billion or lower concentration range, the preparation of scrupulously clean glassware is 

necessary. Failure to do so can lead to a myriad of problems interpreting data due to the 

presence of interferences resulting from contamination. Particular care must be taken with 

glassware such as Soxhlet extractors, Kuderna-Danish evaporative concentrators, 

sampling-train components, or any other glassware that comes into contact with an extract, 

particularly if the extract will be evaporated to a smaller volume. The process of 

concentrating the compounds of interest in this operation may similarly concentrate the 

contaminating substance(s), which may distort the results and complicate data 

interpretation. 

The basic cleaning steps are: 

1. Removal of surface residuals immediately after use; 

2. Hot soak to loosen and float most particulate material; 

3. Hot water rinse to flush away floated particulates; 

4. Soak with an oxidizing agent to destroy traces of organic compounds; 

5. Hot water rinse to flush away materials loosened by the deep penetrant soak; 

6. Distilled water rinse to remove metallic deposits from the tap water; 

7. Alcohol, e.g., isopropanol or methanol, rinse to flush off any final traces of 

organic materials and remove the water; and 

8. Flushing the item immediately before use with some of the same solvent that 

will be used in the analysis. 

Comments regarding each of the eight fundamental steps are discussed here in the 

order in which they appeared above: 

Step 1: As soon as analysis is complete, the glassware (e.g., beakers, pipettes, 

flasks, or bottles) that came into contact with samples or standards 

should be flushed with water and then alcohol or other appropriate 

solvent before it is placed in the hot detergent soak. Otherwise, the soak 

bath may serve to contaminate all other glassware placed therein. 

Step 2: The hot soak consists of a bath of a suitable detergent in water at 50 °C 

or higher. The detergent, powder or liquid, should be entirely synthetic 

and not a fatty acid base. There are very few areas of the country where 

the water hardness is sufficiently low to avoid formation of some 

hard-water scum resulting from the reaction between calcium and 

magnesium salts with a fatty acid soap. This hard-water scum or curd 

would have an affinity particularly for many chlorinated compounds and, 

being almost wholly water-insoluble, would deposit on all glassware in the 

bath in a thin film. 
SW-846 Update V FOUR - 7 Revision 5 

October 2012 

There are many suitable detergents on the wholesale and retail market. 

Most of the common liquid dishwashing detergents sold at retail are 

satisfactory but are more expensive than other comparable products sold 

industrially. Alconox, in powder or tablet form, is manufactured by 

Alconox, Inc., New York, and is marketed by a number of laboratory 

supply firms. Sparkleen, another powdered product, is distributed by 

Fisher Scientific Company. 

Step 3: No comments. 

Step 4: Chromic acid should not be used to clean glassware. Commercial, 

non-chromate products (e.g., Nochromix) may be used in place of 

chromic acid, if adequate cleaning is documented by an analytical quality 

control program. Chromic acid should also not be used with plastic 

bottles. 

The potential hazards of using chromic-sulfuric acid mixture are great and 

have been well publicized. There are now commercially available 

substitutes that possess the advantage of safety in handling. These are 

biodegradable concentrates with a claimed cleaning strength equal to the 

chromic acid solution. They are alkaline, equivalent to roughly 0.1 N 

NaOH upon dilution, and are claimed to remove dried blood, silicone 

greases, distillation residues, insoluble organic residues, etc. They are 

further claimed to remove radioactive traces and will not attack glass or 

exert a corrosive effect on skin or clothing. One such product is "Chem 

Solv 2157," manufactured by Mallinckrodt and available through 

laboratory supply firms. Another comparable product is "Detex," a product 

of Borer-Chemie, Solothurn, Switzerland. Other similarly effective 

products are Nochromix (Godax Laboratories) and Contrad 70 (Decon 

Labs). 

Steps 5, 6, and 7: No comments. 

Step 8: There is always a possibility that between the time of washing and the 

next use, the glassware could pick up some contamination from either the 

air or direct contact. To prevent this, it is good practice to flush the item 

immediately before use with some of the same solvent that will be used in 

the analysis. 

The drying and storage of the cleaned glassware is of critical importance 

to realize the benefit of scrupulous cleaning. Pegboard drying is not 

recommended. It is recommended that laboratory glassware and 

equipment be dried at 100 °C. Under no circumstances should such small 

items be left in the open without protective covering. Otherwise, dust and 

soot in a laboratory environment can re-contaminate the clean glassware. 

As an alternative to solvent rinsing, glassware may be heated to a 

minimum of 300 °C for sufficient time to vaporize any residual organic 

chemicals. Glassware should be allowed to cool fully before use. This 

high temperature treatment should not be used on volumetric glassware, 

glassware with ground glass joints, or sintered glassware. 
SW-846 Update V FOUR - 8 Revision 5 

October 2012 

4.1.7 High concentration samples 

Cross contamination of trace concentration samples may occur when prepared in 

the same laboratory with high concentration samples. Ideally, if both type samples are 

being handled, a laboratory and glassware dedicated solely to the preparation of high 

concentration samples would be available for this purpose. If this is not feasible, as a 

minimum when preparing high concentration samples, disposable glassware should be 

used or, at least, glassware dedicated entirely to the high concentration samples. Avoid 

cleaning glassware used for both trace and high concentration samples in the same area. 
SW-846 Update V FOUR - 9 

TABLE 4-1 

RECOMMENDED SAMPLE CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING T

(Note: Footnotes are located on the last page of the table.) 

VOLATILE ORGANICS

Sample Matrix Container1 Preservative2 

Concentrated waste samples 

Method 5035: See the method. Method 5021: See the method. Methods 5031 and 5032: See the methods. Use PTFE-lined lids for all procedures. 

Cool to ≤6 °C. 

Aqueous samples with no 

residual chlorine present 

Methods 5021, 5030, 5031, and 5032: 2 x 40-mL vials with PTFE-lined septum caps 

Cool to ≤6 °C and adjust pH to less than 2 with 

H2SO4, HCl, or solid NaHSO4

If carbonaceous materials are present, or if MTBE and other fuel oxygenate ethers are present and a high temperature sample preparative method is to be used, do not acid preserve the samples. 

If compounds that readily degrade in acidified water (e.g., 2-chloroethyl vinyl etherb) are 

analytes of interest, collect a second set of samples without acid preservatives and analyze as soon as possible. 
TABLE 4-1 (continued) 

RECOMMENDED SAMPLE CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING T

SW-846 Update V FOUR - 10 

VOLATILE ORGANICS (continued)

Sample Matrix Container1 Preservative2 

Aqueous samples WITH 

residual chlorine present 

Methods 5021, 5030, 5031, and 5032: 2 x 40-mL vials with PTFE-lined septum caps 

Collect sample in a 125-mL container which has been pre-preserved with 4 drops of 10% sodium thiosulfate solution. Gently swirl to mix sample and transfer to a 40-mL VOA vial. Cool to ≤6 °C and adjust pH to less than 2 with 

H2SO4, HCl, or solid NaHSO4. If carbonaceous materials are present, or if 

MTBE and other fuel oxygenate ethers are present and a high temperature sample preparative method is to be used, do not acid preserve the samples. If compounds that readily degrade in acidified water (e.g., 2-chloroethyl vinyl etherb) are 

analytes of interest, collect a second set of samples without acid preservatives and analyze as soon as possible. 

Acrolein and Acrylonitrile 

Aqueous samples 

Methods 5021, 5030, 5031, and 5032: 2 x 40-ml vials with PTFE-lined septum caps 

Adjust to pH 4-5. Cool to ≤6 °C. 

These compounds are highly reactive and should be analyzed as soon as possible. 

Solid samples (e.g. soils, sediments, sludges, ash) 

Method 5035: See the method. Method 5021: See the method. Methods 5031 and 5032: See the methods. 

See the individual methods. If compounds that may be reactive in acidified soils (e.g., vinyl chloride, styrene, 2-chloroethylvinyl ether) are analytes of interest, collect a second set of samples without acid preservatives and analyze as soon as possible. 
TABLE 4-1 (continued) 

RECOMMENDED SAMPLE CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING T

SW-846 Update V FOUR - 11 

SEMIVOLATILE ORGANICS/ORGANOCHLORINE PESTICIDES AND HERBICIDES 

Sample Matrix Container1 Preservative2 

Concentrated waste samples 

125-mL wide-mouth glass with PTFE-lined lid 

Cool to ≤6 °C. 

Aqueous samples with no 

residual chlorine present 

4 x 1-L amber glass container with PTFE-lined lid, or other size, as appropriate, to allow use of entire sample for analysis. 

Cool to ≤6 °C. 

Aqueous samples WITH 

residual chlorine present 

4 x 1-L amber glass container with PTFE-lined lid, or other size, as appropriate, to allow use of entire sample for analysis. 

Add 3-mL 10% sodium thiosulfate solution per 

gallon (or 0.008%). Addition of sodium thiosulfate solution to sample container may be performed in the laboratory prior to field use. Cool to ≤6 °C. 

Solid samples (e.g. soils, sediments, sludges, ash) 

250-mL wide-mouth glass container with PTFE-lined lid 

Cool to ≤6 °C. 
TABLE 4-1 (continued) 

RECOMMENDED SAMPLE CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING T

SW-846 Update V FOUR - 12 

POLYCHLORINATED BIPHENYLS, POLYCHLORINATED DIBENZO-p-DIOXINS, AND POLYCHLORINATED DIBEN

Sample Matrix Container1 Preservative2 

Concentrated waste samples 

125-mL wide-mouth glass with PTFE-lined lid 

None 

Aqueous samples with no 

residual chlorine present 

4 x 1-L amber glass container with PTFE-lined lid, or other size, as appropriate, to allow use of entire sample for analysis. 

Cool to ≤6 °C. 

Aqueous samples WITH 

residual chlorine present 

4 x 1-L amber glass container with PTFE-lined lid, or other size, as appropriate, to allow use of entire sample for analysis. 

Add 3-mL 10% sodium thiosulfate solution per 

gallon (or 0.008%). Addition of sodium thiosulfate solution to sample container may be performed in the laboratory prior to field use. Cool to ≤6 °C 

Solid samples (e.g. soils, sediments, sludges, ash) 

250-mL wide-mouth glass container with PTFE-lined lid. 

Cool to ≤6 °C. 

a The information presented in this table does not represent EPA requirements, but rather it is intended solely as guidance. 

preservation techniques and applicable holding times should be based on the stated project-specific data quality objectives

b See References 1-10 for the preservation and holding times studies for volatile organics and the January and February 2012 RC

discussion for preservation and holding times for vinyl chloride, styrene and 2-chloroethyl vinyl ether in aqueous samples. 1 PTFE lined caps are acceptable for all recommended container types. Additional replicate sample containers should also 

all necessary laboratory quality assurance / quality control audits (e.g., duplicate, matrix spike / matrix spike duplicate QC s

2 The exact sample, extract, and standard storage temperature should be based on project-specific requirements and/or m

recommendations for commercially available standards. Furthermore, alternative storage temperatures may be appropriate analyte stability in a given matrix, provided the stated data quality objectives for a project-specific application are still attain

3 A longer holding time may be appropriate if it can be demonstrated that the reported analyte concentrations are not adve

preservation, storage and analyses performed outside the recommended holding times. 
SW-846 Update V FOUR - 13 Revision 5 

October 2012 

4.2 SAMPLE PREPARATION METHODS 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for 

guidance on the allowed flexibility in the choice of apparatus, reagents, and supplies. In 

addition, unless specified in a regulation, the use of SW-846 methods is not mandatory in 

response to Federal testing requirements. The information contained in each procedure is 

provided by EPA as guidance to be used by the analyst and the regulated community in 

making judgments necessary to meet the data quality objectives or needs for the intended 

use of the data. 

4.2.1 Extractions and preparations 

The following methods are included in this section:

Method 3500C: Organic Extraction and Sample Preparation 

Method 3510C: Separatory Funnel Liquid-Liquid Extraction 

Method 3511: Organic Compounds in Water by Microextraction 

Method 3520C: Continuous Liquid-Liquid Extraction 

Method 3535A: Solid-Phase Extraction (SPE) 

Method 3540C: Soxhlet Extraction 

Method 3541: Automated Soxhlet Extraction 

Method 3542: Extraction of Semivolatile Analytes Collected Using Method 

0010 (Modified Method 5 Sampling Train) 

Method 3545A: Pressurized Fluid Extraction (PFE) 

Method 3546: Microwave Extraction 

Method 3550C: Ultrasonic Extraction 

Method 3560: Supercritical Fluid Extraction of Total Recoverable Petroleum 

Hydrocarbons 

Method 3561: Supercritical Fluid Extraction of Polynuclear Aromatic 

Hydrocarbons 

Method 3562: Supercritical Fluid Extraction of Polychlorinated Biphenyls 

(PCBs) and Organochlorine Pesticides 

Method 3570: Microscale Solvent Extraction (MSE) 

Method 3571: Extraction of Solid and Aqueous Samples for Chemical Agents 

Method 3572: Extraction of Wipe Samples for Chemical Agents 

Method 3580A: Waste Dilution 

Method 3585: Waste Dilution for Volatile Organics 

Method 5000: Sample Preparation for Volatile Organic Compounds 

Method 5021A: Volatile Organic Compounds in Soils and Other Solid Matrices 

Using Equilibrium Headspace Analysis 

Method 5030B: Purge-and-Trap for Aqueous Samples 

Method 5031: Volatile, Non-purgeable, Water-Soluble Compounds by 

Azeotropic Distillation 

Method 5032: Volatile Organic Compounds by Vacuum Distillation 

Method 5035: Closed-System Purge-and-Trap and Extraction for Volatile 

Organics in Soil and Waste Samples 
SW-846 Update V FOUR - 14 Revision 5 

October 2012 

Method 5041A: Analysis for Desorption of Sorbent Cartridges from Volatile 

Organic Sampling Train (VOST) 

4.2.2 Cleanup 

The following methods are included in this section:

Method 3600C: Cleanup 

Method 3610B: Alumina Cleanup 

Method 3611B: Alumina Column Cleanup and Separation of Petroleum Wastes 

Method 3620C: Florisil Cleanup 

Method 3630C: Silica Gel Cleanup 

Method 3640A: Gel-Permeation Cleanup 

Method 3650B: Acid-Base Partition Cleanup 

Method 3660B: Sulfur Cleanup 

Method 3665A: Sulfuric Acid/Permanganate Cleanup 

4.3 DETERMINATION OF ORGANIC ANALYTES 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for 

guidance on the allowed flexibility in the choice of apparatus, reagents, and supplies. In 

addition, unless specified in a regulation, the use of SW-846 methods is not mandatory in 

response to Federal testing requirements. The information contained in each procedure is 

provided by EPA as guidance to be used by the analyst and the regulated community in 

making judgments necessary to meet the data quality objectives or needs for the intended 

use of the data. 

4.3.1 Gas chromatographic methods 

The following methods are included in this section:

Method 8000D: Determinative Chromatographic Separations 

Method 8011: 1,2-Dibromoethane and 1,2-Dibromo-3-chloropropane by 

Microextraction and Gas Chromatography 

Method 8015C: Non-halogenated Organics by Gas Chromatography 

Method 8021B: Aromatic and Halogenated Volatiles by Gas Chromatography 

Using Photoionization and/or Electrolytic Conductivity 

Detectors 

Method 8031: Acrylonitrile by Gas Chromatography 

Method 8032A: Acrylamide by Gas Chromatography 

Method 8033: Acetonitrile by Gas Chromatography with Nitrogen-Phosphorus 

Detection 

Method 8041A: Phenols by Gas Chromatography 

Method 8061A: Phthalate Esters by Gas Chromatography with Electron 

Capture Detection (GC/ECD) 

Method 8070A: Nitrosamines by Gas Chromatography 

Method 8081B: Organochlorine Pesticides by Gas Chromatography 
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Method 8082A: Polychlorinated Biphenyls (PCBs) by Gas Chromatography 

Method 8085: Compound-independent Elemental Quantitation of Pesticides 

by Gas Chromatography with Atomic Emission Detection 

(GC/AED) 

Method 8091: Nitroaromatics and Cyclic Ketones by Gas Chromatography 

Method 8095: Explosives by Gas Chromatography 

Method 8100: Polynuclear Aromatic Hydrocarbons 

Method 8111: Haloethers by Gas Chromatography 

Method 8121: Chlorinated Hydrocarbons by Gas Chromatography: 

Capillary Column Technique 

Method 8131: Aniline and Selected Derivatives by Gas Chromatography 

Method 8141B: Organophosphorus Compounds by Gas Chromatography 

Method 8151A: Chlorinated Herbicides by GC Using Methylation or 

Pentafluorobenzylation Derivatization 

 

4.3.2 Gas chromatographic/mass spectrometric methods 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for 

guidance on the allowed flexibility in the choice of apparatus, reagents, and supplies. In 

addition, unless specified in a regulation, the use of SW-846 methods is not mandatory in 

response to Federal testing requirements. The information contained in each procedure is 

provided by EPA as guidance to be used by the analyst and the regulated community in 

making judgments necessary to meet the data quality objectives or needs for the intended 

use of the data. 

The following methods are included in this section:

Method 8260B: Volatile Organic Compounds by Gas Chromatography/Mass 

Spectrometry (GC/MS) 

Method 8261: Volatile Organic Compounds by Vacuum Distillation in 

Combination with Gas Chromatography/Mass Spectrometry 

(VD/GC/MS) 

Method 8270D: Semivolatile Organic Compounds by Gas 

Chromatography/Mass Spectrometry (GC/MS) 

Method 8275A: Semivolatile Organic Compounds (PAHs and PCBs) in 

Soils/Sludges and Solid Wastes Using Thermal Extraction/Gas 

Chromatography/Mass Spectrometry (TE/GC/MS) 

Method 8280B: Polychlorinated Dibenzo-p-Dioxins (PCDDs) and 

Polychlorinated Dibenzofurans (PCDFs) by High-Resolution 

Gas Chromatography/Low Resolution Mass Spectrometry

(HRGC/LRMS) 

Method 8290A: Polychlorinated Dibenzo-p-dioxins (PCDDs) and 

Polychlorinated Dibenzofurans (PCDFs) by High-Resolution 

Gas Chromatography/High-Resolution Mass Spectrometry 

(HRGC/HRMS) 

Appendix A: Procedures for the Collection, Handling, 
SW-846 Update V FOUR - 16 Revision 5 

October 2012 

Analysis and Reporting of Wipe Tests Performed within the 

Laboratory 

4.3.3 High performance liquid chromatographic methods 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for 

guidance on the allowed flexibility in the choice of apparatus, reagents, and supplies. In 

addition, unless specified in a regulation, the use of SW-846 methods is not mandatory in 

response to Federal testing requirements. The information contained in each procedure is 

provided by EPA as guidance to be used by the analyst and the regulated community in 

making judgments necessary to meet the data quality objectives or needs for the intended 

use of the data. 

The following methods are included in this section:

Method 8310: Polynuclear Aromatic Hydrocarbons 

Method 8315A: Determination of Carbonyl Compounds by High Performance 

Liquid Chromatography (HPLC) 

Appendix A: Re-crystallization of 2,4-Dinitrophenylhydrazine 

(DNPH) 

Method 8316: Acrylamide, Acrylonitrile and Acrolein by High Performance 

Liquid Chromatography (HPLC) 

Method 8318A: N-Methylcarbamates by High Performance Liquid 

Chromatography (HPLC) 

Method 8321B: Solvent-Extractable Nonvolatile Compounds by HighPerformance Liquid Chromatography/Thermospray/Mass 

Spectrometry (HPLC/TS/MS) or Ultraviolet (UV) Detection 

Method 8325: Solvent Extractable Nonvolatile Compounds by High 

Performance Liquid Chromatography/Particle Beam/Mass 

Spectrometry (HPLC/PB/MS) 

Method 8330A: Nitroaromatics and Nitramines by High Performance Liquid 

Chromatography (HPLC) 

Method 8331: Tetrazene by Reverse Phase High Performance Liquid

Chromatography (HPLC) 

Method 8332: Nitroglycerine by High Performance Liquid Chromatography 

4.3.4 Infrared methods 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for 

guidance on the allowed flexibility in the choice of apparatus, reagents, and supplies. In 

addition, unless specified in a regulation, the use of SW-846 methods is not mandatory in 

response to Federal testing requirements. The information contained in each procedure is 

provided by EPA as guidance to be used by the analyst and the regulated community in 

making judgments necessary to meet the data quality objectives or needs for the intended 

use of the data. 
SW-846 Update V FOUR - 17 Revision 5 

October 2012 

The following methods are included in this section:

Method 8410: Gas Chromatography/Fourier Transform Infrared (GC/FT-IR) 

Spectrometry for Semivolatile Organics: Capillary Column 

Method 8430: Analysis of Bis(2-chloroethyl) Ether and Hydrolysis Products by 

Direct Aqueous Injection GC/FT-IR 

Method 8440: Total Recoverable Petroleum Hydrocarbons by Infrared 

Spectrophotometry 

4.3.5 Miscellaneous spectrometric methods 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for 

guidance on the allowed flexibility in the choice of apparatus, reagents, and supplies. In 

addition, unless specified in a regulation, the use of SW-846 methods is not mandatory in 

response to Federal testing requirements. The information contained in each procedure is 

provided by EPA as guidance to be used by the analyst and the regulated community in 

making judgments necessary to meet the data quality objectives or needs for the intended 

use of the data. 

The following method is included in this section: 

 Method 8520: Continuous Measurement of Formaldehyde in Ambient Air 

4.4 IMMUNOASSAY METHODS 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for guidance 

on the allowed flexibility in the choice of apparatus, reagents, and supplies. In addition, unless 

specified in a regulation, the use of SW-846 methods is not mandatory in response to Federal 

testing requirements. The information contained in each procedure is provided by EPA as 

guidance to be used by the analyst and the regulated community in making judgments necessary 

to meet the data quality objectives or needs for the intended use of the data. 

The following methods are included in this section:

Method 4000: Immunoassay 

Method 4010A: Screening for Pentachlorophenol by Immunoassay 

Method 4015: Screening for 2,4-Dichlorophenoxyacetic Acid by 

Immunoassay 

Method 4020: Screening for Polychlorinated Biphenyls by Immunoassay 

Method 4025: Screening for Polychlorinated Dibenzodioxins and 

Polychlorinated Dibenzofurans (PCDD/Fs) by Immunoassay 

Method 4030: Soil Screening for Petroleum Hydrocarbons by Immunoassay 

Method 4035: Soil Screening for Polynuclear Aromatic Hydrocarbons by 

Immunoassay 

Method 4040: Soil Screening for Toxaphene by Immunoassay 

Method 4041: Soil Screening for Chlordane by Immunoassay 
SW-846 Update V FOUR - 18 Revision 5 

October 2012 

Method 4042: Soil Screening for DDT by Immunoassay 

Method 4050: TNT Explosives in Soil by Immunoassay 

Method 4051: Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in Soil by 

Immunoassay 

Method 4425: Screening Extracts of Environmental Samples for Planar 

Organic Compounds (PAHs, PCBs, PCDDs/PCDFs) by a 

Reporter Gene on a Human Cell Line 

Method 4430: Screening For Polychlorinated Dibenzo-p-Dioxins And Furans 

(PCDD/Fs) By Aryl Hydrocarbon-Receptor PCR Assay 

Method 4435: Method For Toxic Equivalents (TEQS) Determinations For 

Dioxin-Like Chemical Activity with the CALUX® Bioassay 

Method 4670: Triazine Herbicides as Atrazine in Water by Quantitative 

Immunoassay 

4.5 MISCELLANEOUS SCREENING METHODS 

Prior to employing the methods in this chapter, analysts are advised to consult the 

disclaimer statement at the front of this manual and the information in Chapter Two for guidance 

on the allowed flexibility in the choice of apparatus, reagents, and supplies. In addition, unless 

specified in a regulation, the use of SW-846 methods is not mandatory in response to Federal 

testing requirements. The information contained in each procedure is provided by EPA as 

guidance to be used by the analyst and the regulated community in making judgments necessary 

to meet the data quality objectives or needs for the intended use of the data. 

The following methods are included in this section:

Method 3815: Screening Solid Samples for Volatile Organics 

Method 3820: Hexadecane Extraction and Screening of Purgeable Organics 

Method 8510: Colorimetric Screening Procedure for RDX and HMX in Soil 

Method 8515: Colorimetric Screening Method for Trinitrotoluene (TNT) in Soil 

Method 8535: Screening Procedure for Total Volatile Organic Halides in 

Water 

Method 8540: Pentachlorophenol by UV-Induced Colorimetry 

Method 9074: Turbidimetric Screening Method for Total Recoverable 

 Petroleum Hydrocarbons in Soil 

Method 9078: Screening Test Method for Polychlorinated Biphenyls in Soil 

Method 9079: Screening Test Method for Polychlorinated Biphenyls in 

Transformer Oil 
SW-846 Update V FOUR - 19 Revision 5 

October 2012 

4.6 REFERENCES 

1. A. B. Dindal, R. A. Jenkins, and C. K. Bayne. "Summary Report - Evaluation of the 

Impact of Post-Holding Time Analyte Degradation on Regulatory Decision-Making - 

VOCs in Water," Oak Ridge National Laboratory. 2001. 

2. ASTM Standard D4841, 1988 (2008). Standard Practice for Estimation of Holding Time 

for Water Samples Containing Organic and Inorganic Constituents. ASTM International, 

West Conshohocken, PA, 2003, DOI: 10.1520/D4841-88R08, www.astm.org

3. J. T. Love, G. C., Deltzer, S. R. Abney, and J. S. Zogorski. “Study Design and Analytical 

Results Used to Evaluate Stability of Volatile Organic Compounds in Water Matrices.” 

United States Geological Survey Open-File Report 98-637. 1999.

4. M. P. Maskarinec, C. K. Bayne, L. H. Johnson, S. K. Holladay, and R. A. Jenkins. 

“Stability of Volatile Organics in Environmental Water Samples: Storage and 

Preservation.” Oak Ridge National Laboratory ORNL/TM-11300. 1989.

5. O. R. West, C. K. Bayne, R. L. Siegrist, W. L. Holden, S. S. Scarborough, and D. W. 

Bottrell. “Stability of VOCs in Water samples During Pre-analytical Holding. Part 1. 

Analyses by a Commercial Laboratory.” Oak Ridge National Laboratory 

ORNL/TM-13240/V1. 1996.

6. O. R. West, C. K. Bayne, R. L. Siegrist, W. L. Holden, and D. W. Bottrell. “Stability of 

VOCs in Water samples During Pre-analytical Holding. Part 2. Analyses by an EPA 

Regional Laboratory.” Oak Ridge National Laboratory ORNL/TM-13240/V2. 1997. 

7. C. K. Bayne, D. D. Schmoyer, and R. A. Jenkins. “Practical Reporting Times for 

Environmental Samples.” Environmental Science and Technology, 28: 1430-1436. 

1994. 

8. M. P. Maskarinec, C. K. Bayne, R. A. Jenkins, L. H. Johnson, and S. K. Holladay. 

“Final Report - Stablity of Volatile Organics in Environmental Soil samples.” Oak Ridge 

National Laboratory ORNL/TM-12128. 1992. 

9. Preservation and Holding Times Study for Vinyl Chloride, Styrene in Industrial 

Wastewater provided by Test America, January 2012. 

10. Preservation and Holding Times Study for Vinyl Chloride, Styrene in Municipal 

Wastewater provided by the Hampton Roads Sanitation District in Virginia Beach, 

Virginia, January 2012. 

11. ASTM Guide D4547, 1991 (2009). Standard Guide for Sampling Waste and Soils for 

Volatile Organic Compounds. ASTM International, West Conshohocken, PA, 2003, 

DOI: 10.1520/D4547-09, www.astm.org

12. U.S. Environmental Protection Agency. “Sample Holding Time Re-evaluation.” 

EPA/600/R-05/124. 2005. 
SW-846 Update V FOUR - 20 Revision 5 

October 2012 

13. U.S. Environmental Protection Agency. “Performance of Hydrochloric Acid and 

Trisodium Phosphate as Preservatives for Selected Organic Compounds in Ground 

Water.” In: A Guide for Assessing Biodegradation and Source Identification of 

Organic Ground Water Contaminants using Compound Specific Isotope Analysis, EPA 

600/R-08/148. 2008. 

14. ASTM Standard Practice D6418, 2003 (2009). Standard Practice for Using the 

Disposable En Core Sample for Sampling and Storing Soil for Volatile Organic 

Analysis. ASTM International, West Conshohocken, PA, 2003, DOI: 

10.1520/D6418-09, www.astm.org

15. RCRA Organic Methods Workgroup Meeting Minutes, January 19, 2012. 

16. RCRA Organic Methods Workgroup Meeting Minutes, January 26, 2012. 

17. RCRA Organic Methods Workgroup Meeting Minutes, February 9, 2012. 

18. U.S. Environmental Protection Agency. “Integrity of VOA Vial Seals.” 

EPA/600/R-00/066. 2000.

 
SW-846 Update V FOUR - 21 Revision 5 

October 2012 

Appendix A: 

 Summary of Updates/Changes in Chapter 4 

1. The document format was updated to Microsoft Word 2007.docx format. 

2. The Revision number was changed to 5. The date published was updated to October 

2012. 

3. Various editorial corrections were made throughout Section 4.1 to 4.5 to improve clarity. 

4. Table 4-1 was reformatted and updated by removing the recommendation to collect a 

second set of samples without adding an acid preservative and analyze in a shorter time 

frame if vinyl chloride and styrene are analytes of concern for aqueous samples. 

5. Methods 3511 and 3572 were added to Section 4.2.1. Various Method version letters 

were updated to the current version. 

6. Methods 4025, 4430 and 4435 were added to Section 4.4 

7. A references section was added as Sec.4.6.